DE3012226A1 - WATER-REPELLENT, AQUE TREATMENT SOLUTIONS - Google Patents

Description

PATE NTAN WALTE

Dlpl.-Ing. P. WIRTH Dr. V. SCH MIE D-KOWARZIK Dlpl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

335024 SIEGFRIEDSTRASSE 8

TELEPHONE: C0891 _{gQQ0 MDNCHEN 40}

March 25, 1980

Wd / wd

Case: A F 62

Koppers Company Inc.
Pittsburgh, PA 15219 / USA

Water-repellent, aqueous treatment solutions.

Ö3006570e0S

j. - ar-

i -3- I

4 y

I The present invention relates to solutions that j

\ Wood and other cellulose products reinforced water-repellent j

j 5 convey abutting properties. In particular, j

j the invention to aqueous cellulose treatment solutions j

i of hexavalent chromium and optionally of copper or j

j copper-arsenic mixtures with aluminum halohydrates in a j

ι Acid medium. According to the invention it has been found that by introducing j

I ίο of aluminum halohydrates in a solution of six- j

; Valuable chromium and possibly copper or copper j f arsenic mixtures are a superior solution for treating
; Wood is made. The solution can be used to treat
r Paper, cardboard and cellulose products are used in general
ί15, although for the sake of simplicity this
] Spelling relates to wood treatment.

I j

\ Copper, chromium and arsenic can be in the solution in the form of j

Compounds are introduced which in aqueous solutions j

Contains J ₂ O for wood treatment and is called "Acid Copper Chromate" j

(ACC) and "Chromated Copper Arsenate" (CCA) are known.
: However, the compounds are preferably selected so that

that they do not contain larger amounts than traces of sulfate ions in S

ί release the aqueous solution for wood treatment. Suitable \

₂₅ compounds include: basic copper carbonate, copper sulphate |

famate, copper nitrate, copper fluorosilicate, copper fluoroborate, j '- cupric oxide or cupric hydroxide, potassium or sodium dichromate, chromium trioxide, arsenic pentoxide, arsenic acid, sodium

arsenate or - pyroarsenate. Sulphate ions are undesirable

;,. since the aluminum halohydrate with an aqueous solution, \ : which has more than a trace or small amount of sulfate ions ent-j

"-. holds, is incompatible and for the formation of precipitation from the \

Solution tends. j

In order to determine the solubility of the aluminum halohydrate in the aqueous J

: gen solution should ensure the amount of chromium,!

Copper and arsenic on the oxide basis 45 wt .-% not exceed \ of the solution. The lower limit, however, can be as low as about
0.5, but is preferably between about 0.8

030065/0605

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and about 14% by weight. The amount of aluminum halohydrate used depends on the concentration of copper, chromium
and arsenic oxide, but is generally from about
0.5 to about 6%, preferably from about 3 to about 6% by weight
the solution. To get good results, the amount is used
of copper, chromium and arsenic oxides, which are present in the solution
is, according to the standard publications of "American Wood
Preserves Association "in Standard Mr. P5-77" for "Acid
ίο Copper Chromat "and" Chromated Copper Arsenate "solutions. The aluminum halohydrates that are used
can include aluminum chlorohydrate, aluminum iodohydrate,
Aluminum bromohydrate and aluminum fluorohydrate.

15 Depending on the connections that are being used, it may

It will be necessary to add a strong acid to dissolve the components of ACC and CCA type B solutions, which at the same time creates the desired pH of the solution
can serve. In general, the pH should be between

about 0.5 and about 5.0, preferably between about 1.2 and I 4.3. Typical acids that can be used! to provide the desired pH include e.g. E.g .: j sulfamic acid, nitric acid, fluorosilicic acid, fluoroboric acid ,! or a mixture of any of these acids with a minor amount of about 2% phosphoric acid. To the invention; To prepare solutions, the compounds j which are added to form the oxides and / or aluminum halohydrate j are preferably diluted before mixing, since the use; concentrated solutions tends to prevent the dissolution of the j components. In general, it is sufficient to j dilute the admixture mixtures to about 0.5 to 14% of oxides, j being about 0.25 to 7% of aluminum halohydrate
contains.

The aluminum halohydrates used according to the invention can, for. B. be represented by the following formula:

Al (OH) X ₅ , wherein X is a halogen such as chlorine, bromine, fluorine or
Iodine, and χ and y integers from 1-4, and ζ an integer
mean from 5-1. As the aluminum halohydrate usually
is polymeric in nature, the invention does not depend on the above
Formula limited. Typical examples of aluminum halogen

0 3 0 0 6 5 / ΟβΟδ

-Jr-S-

hydrates that can be used according to the invention are
for example: Al ₃ OH ₅ Cl ₄ , Al ₉ OH ₁₀ Cl ₂ , Al ₄ OH ₉ Cl ₃ and Al ₂ OH ₄ C

3 According to the invention, any method for treating wood with aqueous treatment solutions can be used. These
Procedures include: treating wood by injecting the
:; aqueous wood treatment solution under pressure in closed ] : containers, dipping in open containers, brushing on the solution or spraying with the solution. According to that!

i method according to the invention for treating wood with a!

; aqueous wood treatment solution can also seal the wood

j send sealed using any type of j

: Sealing that is known to the person skilled in the art and that is j

■ 15 is true, the water-repellent properties of the aqueous j

; Reinforce wood treatment solution. i

; Various alternative embodiments are shown below

the aqueous wood treatment solution according to the invention described 20 ben. In these embodiments, the preferred AIu-
\ mniumhalogenhydrat aluminum chlorohydrate used in 50% aqueous solution. Examples of such solutions that are on the market
; are available are: Wickenol 303 solution, Wickenol 305-
^; Solution and Wickenol 306 solution (all from Wickhen Products
₂₅ Inc., Huguenot, New York). The Wickenol 303 solution is one
aqueous, 50% aluminum chlorohydrate solution with a
Atomic ratio of 2 atoms of Al to 1 atom of chlorine. It can
other products, the atomic ratios of 1 atom of Al to 1 atom of chlorine and atomic ratios between 1 and 2 { ₃₀ aluminum atoms to 1 chlorine atom, can be used. j Ϊ The diluted Wickenol solutions do not show any great water-repellent effect when they are applied as such to the wood. When used in the invention

aqueous wood treatment solutions, however, one achieves one
o _K synergistic effect, which consists in increased water repellency in treated wood.

The following examples serve to illustrate more preferred
Embodiments of the invention. All parts and percentages in the examples, the description and in the

030065 / 06QS

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Claims are based on weight, unless otherwise stated.

Examples

The following solutions were made:

CCA type A

Components

Chromium trioxide

Technical sodium dichromate dihydrate

Basic copper (II) carbonate (55.8% Cu)

73% aqueous arsenic acid deionized water% by weight

100.00%

% Oxide

23.75 23.75 CrO ₃ 13.41 9.00 CrO ₃ 12.96 9.05 CuO 13.87 8.20 As ₂ O ₅ 36.01

50.00%

CCA type B

Components

Chromium trioxide

basic copper (II) carbonate (55.8 % Cu)

75% aqueous arsenic acid technical sulfamic acid Deionized water Wt%

14.12

% Oxide

14.12 CrO ₃

11.22 7th , 84 CuO 29.71 18th , 04 As ₂ O ₅ 5.00 39,: 95

40.00%

100.00 %

Sulphamic acid was added to the solution to prevent ^, that the arsenic acid reacts with part of the copper oxide. J

CCA type C

Components

Chromium trioxide Copper (II) oxide Arsenic pentoxide Deionized water % by weight

23.75 9.25 17.00 50.00

100.00

030 06 5/0 8 oil % Oxide

23.75 CrO ₃ 9.25 CuO 17.00 As ₂ O ₅

50.00%

The three solutions were each used with 3 % of a "Wickenol" aluminum chlorohydrate to treat southern pine sapwood panels to give them water-repellent properties. The plates were treated with the solution under vacuum, allowed to air dry and conditioned for 10 days at a relative humidity of 65% and approx. 24-27 ° C., whereupon the water-repellent properties came through 30 minute immersion in deionized water at room temperature were determined using; the general procedure of the National Wood Manufacturers; Association ("Swellometer Test"). The results are summarized in the following table. j

j

030065/0605

T a b e 1 1 e 1

Aqueous treatment solution

1. 1% oxide CCA-A alone

2. No. 1 with 3 w / w% Wickenol ^{v u} '303

3. No. 1 with 3% w / w Wickenol 305

4. No. 1 with 3 wt / wt% Wickenol

5. 1 ^c / o oxide CCA-B alone

6. No. 5 with 3% w / w Wickenol 303

7. No. 5 with 3% w / w Wickenol 305

8. No. 5 with 3% w / w Wickenol 306

9. 0.8% oxide CCA-C alone

10. No. 9 with 3% Wickenol 303

11. No. 9 with 3% Wickenol 306

12. 1.6% Wickenol 303

13. 1.6% Wickenol 306

Water repellent effectiveness

on the basis of the reduction in

Tangential swelling Water absorption

(A) (B) 54 ί 4 47 65 ί 3 73 68 ί 2 75 72 ί 1 74 7 ί 2 4th 56 ± 1 66 43 ± 1 50 50 ί 1 63

(C)

+
ί
-1
-1

(A)

72 ί 2
75-6

79 ίθ
82 ί 0

-22 ί
72 ί
60 ί

68 ί 2

(B) 65 78 72 75

-20 72 51 65

(C)

-14. 58 ί 37-2

-14

-10

(A) These are panels of boards with a density of 0.585 g / ccm and 11-12% moisture content, used in duplicates and treated up to about 0.601 g / cc of the solution.

(B) These are individual panels of boards with a density of 0.596 g / ccm and 11-12% moisture content, treated up to about 0.673 g / cc of solution.

N? fs)

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(Continuation of the comments on Table 1):

(C) These are individual panels of boards with a density of 0.617g / ccm and 11% moisture content, treated up to about 0.615 g / cc of solution.

(D) Wickenol is the trade name for aluminum chlorine

j hydrate.

From the values it can be seen that the water-repellent effect with the compositions according to the invention in the ver; ¹⁵ equal to the standard solutions or a solution with aluminum halohydrate alone can be considerably strengthened

An additional unexpected property that solutions' of CCA type C (50% liquid oxide concentrate) have achieved through the Addition of aluminum halohydrates is imparted, the- ; those that compatible mixtures prevent the formation of insoluble ί prevent chem green sludge when in contact with wood

come and this especially with an oxide content of 1: 2% as it is normally used in timber treatment will. Attempts have been made in which A heartwood blocks of Douglas fir, each about 19 mm χ in size 38 mm in cylindrical bottles with a capacity of 225 ecm with their long axes in the vertical direction became. Aqueous test solutions were added in quantities so that the pieces of wood floated, but through ■ The constrictions in the bottles below the closures remained fully immersed since the bottles were completely filled became. The well-sealed test bottles were kept at approx. 27 ° C. The results of the observations _ where all test solutions always had a transparent yellow-orange color - are given in the table below.

0 3006 5/0 60 5

oil
σ>
cn

2. 3. 4. 5. 6. 7. 8-

3.0 ° / Ό W-303 - 9 - 5.0 °, Ό Η-303 Original 1.0 ° / Ό W-306 H value 2.0 O ₁ i W-306 co ro
O Ol 3.0 ; i H-305 3.7 5.0 1 / o W-305 3.5 Weight percent in water - 3.4 CCA-C oxides - 3.5 Wickenol type C 3.4 1.0 3.2 2.0 1.9 1.0 1.7 1.0 1.0 2.0 1.0 2.0

Observations of the solutions after 1 week 7 months

stable

stable

stable

stable

stable

stable

unstable

unstable

clear green solution j dark green solution j clear green solution \

dark green solution jν

ι ι pale blue solution j

Cloudy, green-J amber-colored j solution j

j The yellow-orange solution of 1.0 and 2.0% CCA alone j

\ Contact with the wood became cloudy after 3 days, and visible ¹

j green precipitation occurred after a week that ended the i 5 bottom of the container covered. After 7 months the |

\ Precipitate the surfaces and sides of the Douglas fir j

• wooden blocks and the bottoms of the bottles in the experiments NRJ \ 7 and 8. In the experiments, no. 1 - 6 was neither precipitation j

• A green precipitate still appears on the test blocks

io the bottom of the vessels up to a period of 7 months see.

The experiments were carried out using 1% CCA type C ~ 0xide4 alone and with 3% Wickenol 303, 305 and 306, but with ^; 15 60 C repeated. It was found that the 1% oxides; were unstable after heating overnight, and a green precipitate formed i the top and on the sides of the wood blocks. The remaining test solutions remained at I after the test period of 72 hours
; ₂ o stone-like color.

room of 72 hours, stable at 60 C and from a brown-amber

The effect of the Aluminiumhalogenhydrats seems to be the precipitate of the education is in the reduction of hexavalent chromium in contact with timber ₂₅ det the solubilization.

Similar tests were carried out with an ACC solution of the following composition:

ACC type

Ingredients by weight;>% by weight of the oxide

Chromium trioxide 27.5 27.3 CuO ₃

basic copper (ii) carbonate 18.1 12.7 CuO

Sulfamic acid 7.4

35 deionized water 47.0

100.0% 40.0%

Aqueous solutions with oxide concentrations of 5 % or 2% alone and with the addition of various amounts of

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Aluminum chlorohydrate were used for the "swellometer" experiment. The southern pine sapwood panels with a Density of 0.676 g / cc with a moisture content of 11-12% took an average of 0.623 g / cc of the solution at-treatment under vacuum and room temperature. The plates were vacuum treated to about 711 mm Hg exposed, after which the liquid was poured in at room temperature and the plates for 10 minutes at ambient conditions stayed immersed. Then the values of the j. water-repellent properties found that one with j received a 30-minute immersion test of the vacuum-treated panels after drying in air for 7 days.

\ IO Components Table II reduction
tangential
swelling 80 ± 0 water
absorption ACC type with the 2% oxides alone 32 ± 2 68 ± 2 30 ± 5 20 1 No. 1 with 1, 6% Wickenol 303 35 ± 1 75 -2 2. No. 1 with 16 % Wickenol 303 58 ± 2 3. No. 1 with 32 % Wickenol 303 0 ± 4 4th

From the values in the table it can be seen that the inventive Compositions are considerably superior to ACC solutions alone.

f p

\ Solutions of 5.08% sodium dichromate dihydrate (3.41% CrO-) ^!

and 3.41% chromium trioxide (3.41% CrO ^) were tested both as such and with the addition of 3 % of various aluminum chlorohydrates. Solutions 1 - 4 were used with the results below for the treatment of southern pine; Sheets of sapwood were used, and solutions 5-8 were used

Treatment of ponderosa pine sapwood panels used.

The improvement in reducing the tangential! Swelling when using chromium-aluminum chlorohydrate solutions was between about 2 times to multiple ^

Value as shown in Table III. , "" +) IQ ", minutes.- long ~ - - -t · ---

030065/0605

Table III

Solution Effectiveness of reducing tangential swelling. Water absorption

1. 5.08% sodium dichromate dihydrate

2. No. 1 with 3% Wickenol

3. No. 1 with 3% Wickenol A. No. 1 with 3% Wickenol 305>

5. 3, A1% chromium trioxide

6. No. 5 with 3% Wickenol

7. No. 5 with 3% Wickenol

8. No. 5 with 3% Wickenol

6 ί 1 -Α1 1 \ 37 - 3 Α9 ± 1 5Α ± 1 61 ± 1 65 ± 1 68 ± 1
1 6 ±
15 ί 1
1 59 ±
66 ± 1 1Α ± 1 56 ± · ,; 12 ± 1 5Α ±

Claims (1)

Patent claims : 3. Solution according to claim 1-2, characterized in that j the aluminum halohydrate is aluminum chlorohydrate. j ] _{? 0} 4. Solution according to claim 1-3, characterized in that; S the aluminum halohydrate in an amount between about j <0.5 - about 6% by weight, preferably about 3-6% by weight, j ; the solution is present. j ; _{? 5} 5. A solution according to claim 1 - 4, characterized in that j: the pH of about 0.5 - 5.0. j I - 6. Solution according to claims 1-5, characterized in that I ; the oxide (s) are chromium, copper and arsenic _{oxide, chromium, 30} and copper oxide, or just chromium oxide. ^; : 7 · Method of enhancing the water repellency of one
Cellulose material, characterized in that this
with an effective amount of an aqueous acid medium; ;, _{r is} treated in which oxide (s) of hexavalent Chromium and possibly copper and copper-arsenic mixtures and an aluminum halohydrate are dissolved. 030065 / 060S